WO2015036762A1 - Synthèse de nanoparticules de métal-oxyde-semi-conducteur à partir d'un composé agrégat moléculaire - Google Patents

Synthèse de nanoparticules de métal-oxyde-semi-conducteur à partir d'un composé agrégat moléculaire Download PDF

Info

Publication number
WO2015036762A1
WO2015036762A1 PCT/GB2014/052755 GB2014052755W WO2015036762A1 WO 2015036762 A1 WO2015036762 A1 WO 2015036762A1 GB 2014052755 W GB2014052755 W GB 2014052755W WO 2015036762 A1 WO2015036762 A1 WO 2015036762A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecular cluster
metal oxide
recited
nanoparticle
nanoparticles
Prior art date
Application number
PCT/GB2014/052755
Other languages
English (en)
Inventor
Nigel Pickett
Steven Matthew Daniels
Ombretta Masala
Nathalie GRESTY
Original Assignee
Nanoco Technologies Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanoco Technologies Ltd filed Critical Nanoco Technologies Ltd
Priority to EP14767069.9A priority Critical patent/EP3044287B1/fr
Priority to JP2016542370A priority patent/JP6313860B2/ja
Priority to CN201480060625.5A priority patent/CN105705611B/zh
Priority to KR1020177029252A priority patent/KR101883891B1/ko
Priority to KR1020167009529A priority patent/KR101788241B1/ko
Publication of WO2015036762A1 publication Critical patent/WO2015036762A1/fr
Priority to HK16108748.0A priority patent/HK1220717A1/zh

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G13/00—Compounds of mercury
    • C01G13/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
    • H01L29/0657—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape of the body
    • H01L29/0665—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape of the body the shape of the body defining a nanostructure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/26—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, elements provided for in two or more of the groups H01L29/16, H01L29/18, H01L29/20, H01L29/22, H01L29/24, e.g. alloys
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the method relates to the synthesis of metal oxide quantum dots.
  • the method relates to the synthesis of Group IIB oxide quantum dots using a II- VI cluster compound.
  • Metal oxides semiconductors are of increasing technological interest in the electronics industry, for example, for use in field effect transistors (FETs) and transparent conducting oxides (TCOs).
  • FETs field effect transistors
  • TCOs transparent conducting oxides
  • Group IIB oxides find use in laser diodes, as transparent conducting oxides, e.g. in photodiodes, photovoltaic cells, phototransistors, anti-reflective coatings, and in batteries.
  • Quantum dots are luminescent nanoparticles of semiconductor material, with diameters typically in the range of 1 to 20 nm. Their photo-absorption and -luminescence can be tuned by manipulating the particle size.
  • the unique optical and electronic properties of QDs originate from quantum confinement effects; as the QD diameter decreases the electron and hole wavefunctions become quantum confined, giving rise to discrete energy levels similar to those observed in atoms or molecules, resulting in an increase in the semiconductor band gap with decreasing QD diameter.
  • QD materials such as ZnO can become optically transparent, offering advantages for certain applications.
  • ZnO QDs may offer the same level of UV absorption as larger ZnO nanoparticles, but without leaving a white residue on the skin.
  • the high absorption coefficient of QDs enables strong absorption from a tiny amount of material.
  • Omata et al. described the synthesis of 3 - 7 nm ZnO QDs via a combined hydrolysis and successive dehydration condensation reaction between zinc alkoxide and benzylamine.
  • the method produced small, monodisperse nanoparticles with tunable absorption and emission (depending on the reaction temperature), it could only be conducted on a milligram scale.
  • Single-source precursor (SSP) nanoparticle synthesis involves the thermal decomposition of a precursor containing ions of the species to be incorporated into the nanoparticle.
  • SSPs have been used to synthesize metal oxide nanoparticles.
  • ZnO metal oxide nanoparticles.
  • SSP methods typically produce particles with dimensions beyond the QD regime.
  • the majority of prior art methods have not used SSPs to form ZnO in colloidal solutions, so the nanoparticles are often uncapped and thus cannot easily be dispersed in solution for ease of processability.
  • nanoparticles were not isolated from solution and were found to grow and aggregate upon the further application of heat.
  • 2 - 10 nm ZnO nanoparticles have been formed on the surface of multi-wall carbon nanotubes, from the decomposition of a zinc oximato complex [2-(methoxyimino)propanato]zinc(II), at 150°C, [J. Khanderi, R.C. Hoffmann, A. Gurlo and J.J. Schneider, . Mater. Chem., 2009, 19, 5039].
  • a zinc oximato complex [2-(methoxyimino)propanato]zinc(II)
  • CdO is an n-type semiconductor, finding use in optoelectronic devices, phosphors, pigments, as a catalyst and in battery electrodes.
  • 35 nm pseudo-spherical CdO nanoparticles have been fabricated by a photosynthetic route, involving the incubation of aqueous CdCl 2 solution in the presence of a plant ⁇ Achillea wilhelmsii) extract.
  • the first involved a solubility difference method to convert Mg(OH) 2 , in the presence of HgCl 2 and oleic acid, to less soluble Hg(OH) 2 , which decomposed to form 3.0 - 7.4 nm HgO nanoparticles under the reaction conditions.
  • the second method involved the thermolysis of Hg(DDTT) 2 in a furnace to yield 2.4 - 4.8 nm particles. Though the former method generated capped nanoparticles, the size distribution was relatively large, which leads to poor uniformity in the optical properties of the particles. In the latter example, the particles were uncapped and would thus be expected to have poor solubility properties.
  • the molecular cluster compound may be prefabricated.
  • the molecular cluster compound may be generated in situ.
  • the cluster compound may contain (i) ions of both the Group IIB metal and oxygen to be incorporated into the growing nanoparticles, (ii) ions of the Group IIB metal or oxygen, but not both, or (iii) neither ions of oxygen nor the Group IIB metal.
  • the described method may be used to synthesize ZnO, CdO and HgO nanoparticles, including doped and alloyed species thereof.
  • one or more precursors containing a Group IIB metal and oxygen may be added to the colloidal reaction solution.
  • the colloidal reaction solution may include a Lewis base coordinating solvent, or a non-coordinating solvent in conjunction with a ligand to act as a capping agent.
  • an activating agent may be added to the colloidal reaction solution.
  • the colloidal reaction solution is mixed at a first temperature, then heated to a second temperature, or range of temperatures, to initiate nanoparticle growth. The reaction solution is then maintained at elevated temperature to effect nanoparticle growth.
  • the resulting nanoparticles feature a metal oxide semiconductor layer disposed upon the molecular cluster compound.
  • the nanoparticle shape is not restricted and may be a sphere, rod, disc, tetrapod, star or bullet, with a diameter in the range 1 - 100 nm.
  • the nanoparticles are quantum dots (QDs), with diameters in the range 1 - 20 nm, for example, 1 - 10 nm.
  • Figure 1 shows the UV-visible absorption and photoluminescence (PL) spectra of ZnO nanoparticles, synthesized in HDA in the presence of a zinc oximato cluster (Example 1).
  • Figure 2 shows a transmission electron microscopy (TEM) image of ZnO nanoparticles, synthesized in HDA in the presence of a zinc oximato cluster (Example 1), revealing pseudo- spherical particles with diameters ⁇ 10 nm, consistent with nanoparticles in the QD regime.
  • TEM transmission electron microscopy
  • Figure 3 shows the UV-visible absorption spectrum of ZnO nanoparticles, synthesized in HDA/TOPO, using zinc(II) acetate and octanol precursors, in the presence of a zinc oximato cluster (Example 2).
  • Figure 4 shows the UV-visible absorption spectrum of ZnO nanoparticles, synthesized in HDA/TOPO, using zinc(II) acetate and octanol precursors, in the presence of a zinc oximato cluster (Example 3).
  • Figure 5 shows the X-ray diffraction (XRD) pattern of ZnO nanoparticles, synthesized in HDA/TOPO, using zinc(II) acetate and octanol precursors, in the presence of a zinc oximato cluster (Example 3), consistent with zincite phase ZnO. N.B.
  • the low angle (2 ⁇ ⁇ 30°) reflections correspond to the capping agent.
  • Figure 6 shows the UV- visible absorption spectrum of ZnO nanoparticles, synthesized in HDA/TOPO in the presence of a zinc oximato cluster (Example 4).
  • the method described herein relates to the synthesis of Group IIB metal oxide nanoparticles, grown in a colloidal reaction solution in the presence of a II- VI molecular cluster compound, which acts as a seed.
  • a molecular cluster should be understood to mean three or more metal atoms and their associated ligands, having a sufficiently well-defined chemical structure, such that all molecules of the cluster compound possess the same relative molecular formula.
  • the molecular clusters are identical to one another and can be represented by a molecular formula.
  • the molecular cluster seeding method employs a precursor compound containing a first ion and a precursor compound containing a second ion, which react to form nanoparticles in the presence of a population of molecular cluster compounds.
  • the molecular cluster compounds provide "seeds" or nucleation sites at which nanoparticle growth is initiated. As the molecular clusters are all identical (i.e., they all have the same molecular formula) the molecular cluster compounds provide a population of identical nucleation sites.
  • the consistency of the nucleation sites result in a high degree of monodispersity of the resulting nanoparticles.
  • the molecular cluster seeding method obviates the need for a high temperature nucleation step, as required in "hot-injection” techniques.
  • the cluster acts as a template for nanoparticle growth.
  • a key advantage of the molecular seeding method is that it can easily be scaled to produce commercial volumes of QDs, while maintaining a high degree of monodispersity and purity.
  • the molecular seeding method described herein can be used to synthesize nanoparticles in the QD size regime (1 - 20 nm), displaying quantum confinement effects.
  • the method described herein facilitates the production of solution proces sable Group IIB oxide nanoparticles suitable for electronic device applications, both relatively cheaply and on a large scale.
  • the metal oxide nanoparticles prepared as described herein have a metal oxide crystalline core disposed upon the molecular cluster compound.
  • the molecular cluster compound and the resultant nanoparticles have compatible crystallographic phases, to permit the growth of said core nanoparticle material on said molecular cluster.
  • the molecular cluster compound is prefabricated, prior to its addition to the reaction solution.
  • the molecular cluster compound is generated in situ, prior to the addition of precursors used to effect particle growth.
  • the conversion of the precursor(s) to the nanoparticle material can be conducted in any suitable solvent.
  • the temperature of the solvent must be sufficiently high to ensure satisfactory dissolution and mixing of the cluster compound (it is desirable, but not necessary that the present compounds are fully dissolved), but not so high as to disrupt the integrity of the cluster compound molecules.
  • the temperature of the solution thus formed is raised to a temperature, or range of temperatures, which is/are sufficiently high to initiate nanoparticle growth. As the temperature is increased, further quantities of precursor may be added to the reaction in a dropwise manner, or as a solid or gas. The solution can then be maintained at this temperature or within this temperature range for as long as required to form nanoparticles possessing the desired properties.
  • a wide range of appropriate solvents is available.
  • the particular solvent used is usually at least partly dependent upon the nature of the reacting species, i.e. nanoparticle precursor(s) and/or cluster compound, and/or the type of nanoparticles that are to be formed.
  • Typical solvents include Lewis base-type coordinating solvents, such as a phosphine, e.g. trioctylphosphine (TOP), a phosphine oxide, e.g. trioctylophosphine oxide (TOPO), an amine, e.g. hexadecylamine (HDA), or a thiol, e.g.
  • octanethiol or non-coordinating organic solvents, e.g. alkanes and alkenes, polyelectrolytes such as poly(acrylic acid), polyalylamines, or diethylene glycol. If a non-coordinating solvent is used then the reaction will usually proceed in the presence of a further coordinating agent to act as a "capping agent".
  • non-coordinating organic solvents e.g. alkanes and alkenes, polyelectrolytes such as poly(acrylic acid), polyalylamines, or diethylene glycol.
  • organically-capped colloidal QD cores generally display a low photoluminescence quantum yield (QY), due to exciton recombination via surface defects and dangling bonds.
  • QY photoluminescence quantum yield
  • Modification of the structural and electronic architecture of the QDs, while maintaining control of the size-tunable band gap, can be achieved via the epitaxial growth of one or more "shell" layers of different band gap semiconductor material(s) on the nanoparticle surface.
  • a core/shell architecture is achieved by the growth of a wider band gap material on the core surface, e.g. CdO/ZnO. Shelling serves to eliminate surface defects and dangling bonds to significantly improve the QY and enhance stability by suppressing interactions between charge carriers and the surrounding environment.
  • shelling layers as in the core/multishell structure, e.g. CdO/ZnSe/ZnO, a quantum dot-quantum well architecture, e.g. ZnO/CdO/ZnO, or a core/compositionally graded shell structure, e.g. CdO/Cdi_ x Zn x Sei_ y O y .
  • QD synthesis may proceed in the presence of an activating agent to lower the decomposition temperature of the molecular cluster.
  • Suitable activating agents include, but are not restricted to, alcohols, such as octanol, and amines, such as HDA.
  • particle growth can be monitored by taking aliquots from the reaction solution and measuring the UV- visible absorption and/or PL spectra.
  • the shape of the nanoparticles may consist of a sphere, rod, disc, tetrapod, star or bullet, but is not restricted to these.
  • the nanoparticle shape can be controlled via any means known to one skilled in the art, such as by modifying the reaction ligands and/or processing conditions.
  • the method describes the synthesis of Group IIB metal oxide nanoparticles: ZnO, CdO and HgO, including doped species and alloys thereof.
  • ZnO nanoparticles can be grown in the presence of a cluster compound containing zinc and oxygen, such as diaquabis[2-(methoximino)propanato]zinc(II), [Zn(OC(0)C(Me)N(OMe)) 2 ]-2H 2 0.
  • a cluster compound containing zinc and oxygen such as diaquabis[2-(methoximino)propanato]zinc(II), [Zn(OC(0)C(Me)N(OMe)) 2 ]-2H 2 0.
  • CdO nanoparticles can be grown in the presence of a cluster compound containing cadmium and sulphur, such as [Et 3 NH]4[Cd 1 oS4(SPh) 16 ].
  • II ⁇ M 1 that the M contained within the molecular cluster is not the same M as contained in the oxide MO.
  • CdO nanoparticles can be grown in the presence of a cluster compound containing zinc and oxygen, such as diaquabis[2-(methoximino)propanato]zinc(II), [Zn(OC(0)C(Me)N(OMe)) 2 ] ⁇ 2H 2 0.
  • the metal oxide nanoparticles are grown in the presence of a II- VI cluster where II ⁇ M 1 and VI ⁇ O.
  • HgO nanoparticles can be grown in the presence of a cluster compound containing cadmium and selenium, such as [Et 3 NH]4[Cd 1 oSe 4 (SPh) 1 6] .
  • the metal oxide nanoparticles are grown in the presence of a II- VI cluster, as described in embodiments 1 - 4, where the cluster contains ions of more than one Group IIB metal and/or more than one chalcogen to form doped or alloyed nanoparticles. Examples include, but are not restricted to, Zni_ x Cd x O and ZnOi_ y S y .
  • the metal oxide nanoparticles are grown in the presence of a II- VI cluster, as described in embodiments 1 - 4, and in the presence of additional metal ions to form doped metal oxide nanoparticles.
  • the dopant metal may be from Group IIB of the periodic table, but may also be from any other group.
  • nanoparticle material include, but are not restricted to, ZnO:Al and CdO:In.
  • one or more layers of semiconductor material may be grown epitaxially on the surface of the metal oxide nanoparticles to form a shell, to eliminate surface defects and dangling bonds in order to improve the fluorescence QY and enhance stability by suppressing interactions between charge carriers and the surrounding environment.
  • the shell material(s) will, in most cases, be of a similar lattice type to the core material, i.e. each shell material will have close lattice match to the core material so that it can be epitaxially grown on to the core, but the shell materials are not necessarily restricted to this compatibility.
  • the material(s) used for any shell(s) grown onto the core will, in most cases, have a wider band gap than the core material, but is/are not necessarily restricted to materials of this compatibility.
  • Suitable shell materials include, but are not restricted to:
  • Nanoparticle material includes, but is not restricted to, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe.
  • IIB-VIB (12-16) material consisting of a first element from group 12 of the periodic table and a second element from group 16 of the periodic table, and also including ternary, quaternary and doped materials thereof.
  • Nanoparticle material includes, but is not restricted to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe.
  • II- V material consisting of a first element from group 12 of the periodic table and a second element from group 15 of the periodic table, and also including ternary, quaternary and doped materials thereof.
  • Nanoparticle material includes, but is not restricted to, Zn 3 N 2 , Zn 3 P 2 , Zn 3 As 2 , Cd 3 N 2 , Cd 3 P 2 , Cd 3 As 2 .
  • III-V material consisting of a first element from group 13 of the periodic table and a second element from group 15 of the periodic table, and also including ternary, quaternary and doped materials thereof.
  • Nanoparticle material includes, but is not restricted to, BN, BP, A1N, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb.
  • III- IV material consisting of a first element from group 13 of the periodic table and a second element from group 14 of the periodic table, and also including ternary, quaternary and doped materials thereof.
  • Nanoparticle material includes, but is not restricted to, B 4 C, A1 4 C 3 ,
  • III- VI material consisting of a first element from group 13 of the periodic table and a second element from group 16 of the periodic table, and also including ternary, quaternary and doped materials thereof.
  • Nanoparticle material includes, but is not restricted to, AI 2 S 3 , Al 2 Se 3 , Al 2 Te 3 , Ga 2 S 3 , Ga 2 Se 3 , Ga 2 Te 3 , In 2 S 3 , In 2 Se 3 , In 2 Te 3 .
  • IV- VI material consisting of a first element from group 14 of the periodic table and a second element from group 16 of the periodic table, and also including ternary, quaternary and doped materials thereof.
  • Nanoparticle material includes, but is not restricted to, PbS, PbSe, PbTe, SnS, SnSe, SnTe.
  • Nanoparticle material consisting of a first element from the d-block of the periodic table and a second element from group 16 of the periodic table, and also including ternary, quaternary and doped materials thereof.
  • Nanoparticle material includes, but is not restricted to, NiS, CrS, CuInS 2 , CuInSe 2 , AgInS 2 .
  • the outermost surface of the nanoparticles is capped with a layer of organic ligands, known as a "capping agent".
  • the capping agent passivates the nanoparticle surface to eliminate surface defects and dangling bonds, and imparts solubility to thus facilitate solution processing of the nanoparticles.
  • Such capping agents are typically Lewis bases, including mono- or multi-dentate ligands of the type phosphines (e.g. TOP, triphenolphosphine, i-butylphosphine), phosphine oxides (e.g. TOPO), alkyl phosphonic acids, alkylamines (e.g.
  • HDA high-density polyethylene glycol
  • octylamine arylamines
  • pyridines e.g. pyridines
  • thiols e.g. octanethiol
  • a long chain fatty acid e.g. thiophenes
  • other agents such as oleic acid and organic polymers that form protective sheaths around the nanoparticles.
  • the method described herein is used to fabricate nanoparticles with a homogeneous shape and size distribution.
  • the nanoparticle shape may consist of, but is not restricted to, a sphere, rod, disc, tetrapod, star or bullet.
  • the nanoparticle morphology can be controlled using any means known to one skilled in the art, such as modification to the reaction conditions or ligand(s).
  • the nanoparticle diameter (along its shortest axis) lies in the range 1 - 100 nm, more preferably 1 - 20 nm, most preferably 1 - 10 nm.
  • a pre-fabricated cluster compound is mixed with a high boiling solvent.
  • appropriate precursors are added to the solvent to form a molecular cluster in situ.
  • a capping agent is added to the reaction solution.
  • additional metal and oxide precursors are added, either in the form of separate precursors or as a single-source precursor.
  • Any suitable molar ratio of the molecular cluster material to the metal and oxide precursor(s) may be employed. Preferably, the molar ratio lies in the range 1:0 (i.e. no metal and oxide precursor(s) to 1: 10,000, more preferably 1:0 to 1: 1,000, and most preferably 1:0 to 1:250.
  • an activating agent is added to the reaction solution to lower the decomposition temperature of the cluster.
  • the reagents are stirred at a first temperature that is sufficiently low that no particle growth will occur.
  • the solution is then heated, at a steady rate, to a second temperature at which particle growth is initiated.
  • further quantities of the metal and oxide precursors may be added to sustain particle growth and to inhibit particles from being consumed via Ostwald's ripening.
  • the reaction is quenched by cooling the solution.
  • the preparative procedure comprises the growth of Group IIB metal oxide nanoparticles in the presence of a II- VI molecular cluster compound.
  • a II- VI molecular cluster compound examples include:
  • the cluster compound contains the Group IIB metal (M) and oxygen (O) ions to be incorporated into the metal oxide (MO) nanoparticles.
  • the cluster compound contains either Group IIB metal (M) or oxygen (O) ions to be incorporated into the metal oxide (MO) nanoparticles, but not both.
  • the cluster compound contains neither the Group IIB metal (M) or oxygen (O) ions to be incorporated into the metal oxide (MO) nanoparticles.
  • the II- VI cluster contains oxygen.
  • suitable cluster compounds include, but are not restricted to: oximato clusters, e.g. [Zn(OC(0)C(Me)N(OMe)) 2 ] ⁇ 2H 2 0.
  • the II- VI cluster contains sulfur.
  • the II- VI cluster contains selenium.
  • the II- VI cluster contains tellurium.
  • the Group IIB metal (M) precursor may include, but is not restricted to, an organometallic compound, an inorganic salt, a coordination compound, or an elemental source.
  • the metal precursor also acts as a source of oxygen (e.g. when the metal precursor is a fatty acid salt such as a metal stearate), no additional oxygen-containing precursor may be required.
  • the metal precursor may be added in conjunction with an oxygen source that may include, but is not restricted to, a peroxide, a base, an inorganic salt, a coordination compound, an alcohol, or elemental oxygen. Specific examples include, but are not restricted to: peroxides, e.g. H 2 0 2 ; bases such as a hydroxide, e.g. NaOH; inorganic salts such as Na 2 0; coordination compounds such as N0 2 ; alcohols such as primary, secondary or tertiary alcohols.
  • Dopant Source(s) [0071] Where the nanoparticles comprise a doped of alloyed Group IIB metal oxide-containing material, one or more dopant sources can be provided by any appropriate compound known to one skilled in the art, including one or more molecular cluster compounds. The dopant source(s) may be added to the reaction solution in the solid, liquid and/or gaseous phases.
  • Suitable reaction solvents include, but are not restricted to, Lewis base-type coordinating solvents, such as a phosphine (e.g. TOP), a phosphine oxide (e.g. TOPO), or an amine (e.g. HDA), or non-coordinating organic solvents, such as an alkane, an alkene (e.g. 1-octadecene), or heat transfer fluid (e.g. Therminol® 66).
  • Lewis base-type coordinating solvents such as a phosphine (e.g. TOP), a phosphine oxide (e.g. TOPO), or an amine (e.g. HDA)
  • non-coordinating organic solvents such as an alkane, an alkene (e.g. 1-octadecene), or heat transfer fluid (e.g. Therminol® 66).
  • a capping agent When nanoparticle growth is conducted in a non-coordinating solvent, a capping agent must be added to the reaction solution.
  • Such capping agents are typically Lewis bases, including mono- or multi-dentate ligands of the type phosphines (e.g. TOP, triphenolphosphine, t- butylphosphine), phosphine oxides (e.g. TOPO), alkyl phosphonic acids, alkylamines (e.g. HDA, octylamine), arylamines, pyridines, thiols (e.g. octanethiol), a long chain fatty acid, and thiophenes, but a wide range of other agents are available, such as oleic acid and organic polymers that form protective sheaths around the nanoparticles.
  • phosphines e.g. TOP, triphenolphosphine, t- butylphosphine
  • the outermost layer (capping agent) of a QD can consist of a coordinated ligand that processes additional functional groups that can be used as chemical linkage to other inorganic, organic or biological material, whereby the functional group is pointing away from the QD surface and is available to bond/react with other available molecules, such as, but not restricted to, primary and/or secondary amines, alcohols, carboxylic acids, azides, hydroxyl group, etc.
  • the outermost layer (capping agent) can also consist of a coordinated ligand that processes a functional group that is polymerisable and can be used to form a polymer around the particle.
  • the outermost layer can also consist of organic units that are directly bonded to the outermost inorganic layer and can also possess a functional group, not bonded to the surface of the particle, which can be used to form a polymer around the particle, or for further reactions.
  • the QD synthesis is conducted in the presence of an activating agent to lower the decomposition temperature of the molecular cluster compound and thus promote nanoparticle growth at lower temperature.
  • an activating agent known to one skilled in the art may be used including, but not restricted to, an alcohol, e.g. octanol, or an amine, e.g. HDA, octylamine, etc.
  • the activating agent is HDA.
  • a method of forming metal oxide nanoparticles comprising: reacting nanoparticle precursors comprising a metal and oxygen in in the presence of a population of molecular cluster compounds.
  • the molecular cluster compounds and the metal oxide nanoparticles may share a crystallographic phase.
  • the molecular cluster compounds may be fabricated in situ.
  • the molecular cluster compounds may be II- VI molecular cluster compounds.
  • Both the molecular cluster compounds and the metal oxide nanoparticle precursors may comprise identical Group IIB metals and oxygen.
  • the molecular cluster compounds may not comprise oxygen.
  • the molecular cluster compounds may not comprise a Group IIB metal identical to a metal of the nanoparticle precursors.
  • the cluster compounds may be oximato clusters.
  • the metal oxide nanoparticles may comprise a Group IIB metal.
  • the metal oxide nanoparticles may comprise ZnO, CdO or HgO.
  • the metal oxide nanoparticles may be doped or alloyed with atoms of the molecular cluster compounds.
  • the metal oxide nanoparticles may be grown on the molecular cluster compounds.
  • the metal oxide nanoparticle precursors may comprise a Group IIB metal and oxygen.
  • the Group IIB metal and oxygen may be added as a single-source precursor.
  • the reacting may comprise reacting the nanoparticle precursors in the presence of an activating agent.
  • the metal oxide nanoparticles may be quantum dots.
  • a second aspect of the present invention provides a nanoparticle comprising a metal oxide crystalline core disposed upon a molecular cluster compound.
  • the molecular cluster compound and the metal oxide core may share a crystallographic phase.
  • the molecular cluster compound may be II- VI molecular cluster compounds. Both the molecular cluster compound and the metal oxide crystalline core may comprise identical Group IIB metals and oxygen. The molecular cluster compound may not comprise oxygen. The molecular cluster compound may not comprise a Group IIB metal identical to a metal of the metal oxide crystalline core.
  • Example 1 Synthesis of ZnO Nanoparticles in Hexadecylamine.
  • HDA (10 g, 41 mmol) was degassed under vacuum at 120°C.
  • Diaquabis[2-(methoxyimino)propanato]zinc(II) cluster (100 mg, 0.30 mmol) was added, dissolving immediately to form a clear solution.
  • the temperature was increased to 150°C and held for 30 minutes.
  • the temperature was increased to 200°C and held for 30 minutes, before cooling the solution to room temperature.
  • UV a b s ⁇ 355 nm; PLmax 370 nm ( Figure 1).
  • Transmission electron microscopy (TEM, Figure 2) imaging reveals pseudo-spherical particles with diameters ⁇ 10 nm, consistent with nanoparticles in the quantum dot regime.
  • Example 2 Synthesis of ZnO Nanoparticles in Hexadecylamine and Trioctylphosphine Oxide, using Zinc Acetate and Octanol Precursors.
  • HDA 7 g, 29 mmol
  • TOPO 3 g, 7.8 mmol
  • Diaquabis[2- (methoxyimino)propanato]zinc(II) cluster 100 mg, 0.30 mmol
  • the temperature was decreased to 75 °C and the solution was annealed for 2 1 ⁇ 2 hours, before cooling to room temperature overnight.
  • Example 3 Concentrated Synthesis of ZnO Nanoparticles in Hexadecylamine and Trioctylphosphine Oxide, using Zinc Acetate and Octanol Precursors.
  • HDA 7 g, 29 mmol
  • TOPO 3 g, 7.8 mmol
  • diaquabis[2-(methoxyimino)propanato]zinc(II) cluster 200 mg, 0.60 mmol
  • zinc(II) acetate 200 mg, 1.1 mmol
  • Example 4 Synthesis of ZnO Nanoparticles in Hexadecylamine and Trioctylphosphine Oxide.
  • HDA 7 g, 29 mmol
  • TOPO 3 g, 7.8 mmol
  • diaquabis[2- (methoxyimino)propanato]zinc(II) cluster was added and the solution was subsequently heated to 200°C in 20 minutes. The temperature was held for 40 minutes, before cooling the solution to 70°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un procédé de préparation de nanoparticules d'oxyde métallique. Le procédé consiste à faire réagir des précurseurs de nanoparticules en présence d'une population de composés agrégats moléculaires. Le composé agrégat moléculaire peut contenir ou non le même métal qui sera présent dans la nanoparticule d'oxyde métallique. De la même manière, le composé agrégat moléculaire peut contenir ou non de l'oxygène. Les composés agrégats moléculaires agissent comme germes ou matrices sur lesquels est initiée la croissance des nanoparticules. Comme tous les composés agrégats moléculaires sont identiques, les sites de nucléation identiques conduisent à des populations hautement monodisperses de nanoparticules d'oxyde métallique.
PCT/GB2014/052755 2013-09-13 2014-09-11 Synthèse de nanoparticules de métal-oxyde-semi-conducteur à partir d'un composé agrégat moléculaire WO2015036762A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP14767069.9A EP3044287B1 (fr) 2013-09-13 2014-09-11 Synthèse de nanoparticules de métal-oxyde-semi-conducteur à partir d'un composé agrégat moléculaire
JP2016542370A JP6313860B2 (ja) 2013-09-13 2014-09-11 分子クラスタ化合物からの金属酸化物ナノ粒子の合成
CN201480060625.5A CN105705611B (zh) 2013-09-13 2014-09-11 自分子簇化合物合成金属氧化物半导体纳米粒子
KR1020177029252A KR101883891B1 (ko) 2013-09-13 2014-09-11 분자 클러스터 화합물로부터 금속 산화물 반도체 나노 입자의 합성
KR1020167009529A KR101788241B1 (ko) 2013-09-13 2014-09-11 분자 클러스터 화합물로부터 금속 산화물 반도체 나노 입자의 합성
HK16108748.0A HK1220717A1 (zh) 2013-09-13 2016-07-21 由分子簇合物合成的金屬氧化物半導體納米粒子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361877787P 2013-09-13 2013-09-13
US61/877,787 2013-09-13

Publications (1)

Publication Number Publication Date
WO2015036762A1 true WO2015036762A1 (fr) 2015-03-19

Family

ID=51570761

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2014/052755 WO2015036762A1 (fr) 2013-09-13 2014-09-11 Synthèse de nanoparticules de métal-oxyde-semi-conducteur à partir d'un composé agrégat moléculaire

Country Status (8)

Country Link
US (1) US20150076494A1 (fr)
EP (1) EP3044287B1 (fr)
JP (2) JP6313860B2 (fr)
KR (2) KR101788241B1 (fr)
CN (2) CN105705611B (fr)
HK (1) HK1220717A1 (fr)
TW (3) TWI655156B (fr)
WO (1) WO2015036762A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271361A (zh) * 2015-10-28 2016-01-27 中国科学院上海微系统与信息技术研究所 一种树枝状氧化锌纳米线阵列的制备方法
CN105271362A (zh) * 2015-10-31 2016-01-27 合肥师范学院 一种具有花瓣效应的ZnO纳米结构的制备方法
US9780266B2 (en) 2015-06-30 2017-10-03 Cree, Inc. Stabilized quantum dot structure and method of making a stabilized quantum dot structure
US10347799B2 (en) 2017-11-10 2019-07-09 Cree, Inc. Stabilized quantum dot composite and method of making a stabilized quantum dot composite
WO2020154511A1 (fr) * 2019-01-23 2020-07-30 University Of Washington Points quantiques de phosphure d'indium, grappes et procédés associés
US10851298B2 (en) 2018-08-30 2020-12-01 Samsung Electronics Co., Ltd. Electronic device including quantum dots
US10978657B2 (en) 2018-08-23 2021-04-13 Samsung Electronics Co., Ltd. Quantum dot device and quantum dots
US11499098B2 (en) 2019-08-29 2022-11-15 Samsung Electronics Co., Ltd. Quantum dots and device including the same
US11917841B2 (en) 2019-12-16 2024-02-27 Samsung Electronics Co., Ltd. Light-emitting device comprising organic salt bound to quantum dots and production method thereof
US11925043B2 (en) 2019-10-18 2024-03-05 Samsung Electronics Co., Ltd. Quantum dot light-emitting device and electronic device

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9738799B2 (en) * 2014-08-12 2017-08-22 Purdue Research Foundation Homogeneous precursor formation method and device thereof
US9340461B1 (en) * 2014-11-24 2016-05-17 Ut-Battelle, Llc Method of making controlled morphology metal-oxides
CN106010524B (zh) * 2016-05-24 2018-12-28 浙江大学 Iii-v族量子点、其制备方法及其应用
TWI636120B (zh) * 2017-08-04 2018-09-21 奇美實業股份有限公司 量子點的製造方法、發光材料、發光元件以及顯示裝置
CN111326661B (zh) * 2018-12-13 2022-08-02 纳晶科技股份有限公司 掺杂氧化锌纳米晶及其制备方法、量子点发光器件及其制备方法
KR102718278B1 (ko) 2019-10-24 2024-10-15 삼성전자주식회사 전계 발광 소자 및 이를 포함하는 표시 장치
KR20220003356A (ko) 2020-07-01 2022-01-10 삼성전자주식회사 발광 소자 및 이를 포함하는 표시 장치
KR20220022517A (ko) * 2020-08-18 2022-02-28 삼성디스플레이 주식회사 반도체 나노입자 및 이를 포함한 전자 장치

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080220593A1 (en) * 2005-08-12 2008-09-11 Nanoco Technologies Limited Nanoparticles
US20110068322A1 (en) * 2009-09-23 2011-03-24 Nanoco Technologies Limited Semiconductor Nanoparticle-Based Materials

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1894799A (zh) 2003-09-05 2007-01-10 点度量技术有限公司 具有纳米级外延过生长的量子点光电器件以及制造方法
US7588828B2 (en) * 2004-04-30 2009-09-15 Nanoco Technologies Limited Preparation of nanoparticle materials
GB0409877D0 (en) * 2004-04-30 2004-06-09 Univ Manchester Preparation of nanoparticle materials
TW200716698A (en) * 2005-10-03 2007-05-01 Kaneka Corp Transparent polymer nanocomposites containing nanoparticles and method of making same
GB0522027D0 (en) * 2005-10-28 2005-12-07 Nanoco Technologies Ltd Controlled preparation of nanoparticle materials
GB0714865D0 (en) * 2007-07-31 2007-09-12 Nanoco Technologies Ltd Nanoparticles
KR101813688B1 (ko) * 2007-09-28 2017-12-29 나노코 테크놀로지스 리미티드 코어 쉘 나노입자들 및 이들의 준비 방법
JP5388099B2 (ja) * 2007-12-28 2014-01-15 国立大学法人大阪大学 コアシェル型量子ドット蛍光微粒子
US20120251450A1 (en) 2011-04-04 2012-10-04 Alex Punnoose Nanoparticles that preferentially associate with and kill diseased cells for diagnostic and therapeutic applications

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080220593A1 (en) * 2005-08-12 2008-09-11 Nanoco Technologies Limited Nanoparticles
US20110068322A1 (en) * 2009-09-23 2011-03-24 Nanoco Technologies Limited Semiconductor Nanoparticle-Based Materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FABIEN GRASSET ET AL: "When "Metal Atom Clusters" Meet ZnO Nanocrystals: A ((n-C4H9)4N)2Mo6Br14@ZnO Hybrid", ADVANCED MATERIALS, vol. 20, no. 9, 5 May 2008 (2008-05-05), pages 1710 - 1715, XP055152121, ISSN: 0935-9648, DOI: 10.1002/adma.200701845 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9780266B2 (en) 2015-06-30 2017-10-03 Cree, Inc. Stabilized quantum dot structure and method of making a stabilized quantum dot structure
CN105271361A (zh) * 2015-10-28 2016-01-27 中国科学院上海微系统与信息技术研究所 一种树枝状氧化锌纳米线阵列的制备方法
CN105271362A (zh) * 2015-10-31 2016-01-27 合肥师范学院 一种具有花瓣效应的ZnO纳米结构的制备方法
US10879433B2 (en) 2017-11-10 2020-12-29 Cree, Inc. Stabilized quantum dot composite and method of making a stabilized quantum dot composite
US10347799B2 (en) 2017-11-10 2019-07-09 Cree, Inc. Stabilized quantum dot composite and method of making a stabilized quantum dot composite
US10978657B2 (en) 2018-08-23 2021-04-13 Samsung Electronics Co., Ltd. Quantum dot device and quantum dots
US11569468B2 (en) 2018-08-23 2023-01-31 Samsung Electronics Co., Ltd. Quantum dot device and quantum dots
US12041802B2 (en) 2018-08-23 2024-07-16 Samsung Electronics Co., Ltd. Quantum dot device and quantum dots
US10851298B2 (en) 2018-08-30 2020-12-01 Samsung Electronics Co., Ltd. Electronic device including quantum dots
US11060026B2 (en) 2018-08-30 2021-07-13 Samsung Electronics Co., Ltd. Electronic device including quantum dots
WO2020154511A1 (fr) * 2019-01-23 2020-07-30 University Of Washington Points quantiques de phosphure d'indium, grappes et procédés associés
US11499098B2 (en) 2019-08-29 2022-11-15 Samsung Electronics Co., Ltd. Quantum dots and device including the same
US11981851B2 (en) 2019-08-29 2024-05-14 Samsung Electronics Co., Ltd. Quantum dots and device including the same
US11925043B2 (en) 2019-10-18 2024-03-05 Samsung Electronics Co., Ltd. Quantum dot light-emitting device and electronic device
US11917841B2 (en) 2019-12-16 2024-02-27 Samsung Electronics Co., Ltd. Light-emitting device comprising organic salt bound to quantum dots and production method thereof

Also Published As

Publication number Publication date
CN105705611A (zh) 2016-06-22
HK1220717A1 (zh) 2017-05-12
CN108751248A (zh) 2018-11-06
KR101883891B1 (ko) 2018-08-30
CN108751248B (zh) 2021-02-26
TW201514101A (zh) 2015-04-16
JP6570688B2 (ja) 2019-09-04
JP2018135266A (ja) 2018-08-30
TWI655156B (zh) 2019-04-01
TW201827344A (zh) 2018-08-01
KR20160055237A (ko) 2016-05-17
KR101788241B1 (ko) 2017-10-19
JP6313860B2 (ja) 2018-04-18
CN105705611B (zh) 2018-06-29
EP3044287B1 (fr) 2018-09-12
TWI661993B (zh) 2019-06-11
TW201641428A (zh) 2016-12-01
KR20170117619A (ko) 2017-10-23
US20150076494A1 (en) 2015-03-19
TWI557076B (zh) 2016-11-11
JP2016539908A (ja) 2016-12-22
EP3044287A1 (fr) 2016-07-20

Similar Documents

Publication Publication Date Title
EP3044287B1 (fr) Synthèse de nanoparticules de métal-oxyde-semi-conducteur à partir d'un composé agrégat moléculaire
EP2970763B1 (fr) Points quantiques créés à l'aide de phosphine
JP6114369B2 (ja) ナノ粒子
KR101342684B1 (ko) 나노입자의 제조
TWI649266B (zh) 分層過渡金屬二硫族化物奈米粒子之溶液相合成
JP2018065738A (ja) ナノ粒子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14767069

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016542370

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2014767069

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014767069

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20167009529

Country of ref document: KR

Kind code of ref document: A